Cyclopropane carboxylic acid ester derivatives

ABSTRACT

Cyclopropane carboxylic acid ester derivatives and optical and geometrical isomers thereof expressed by the general formula: ##STR1## wherein R 1  represents hydrogen atom or methyl group, R 2  represents alkyl group, alkenyl group, haloalkyl group, haloalkenyl group having 1-6 carbon atoms and a group selected from the groups of the general formulae (II), (III) and (IV): ##STR2## in which n is an integer of 2-5, R 4  represents methyl group, chlorine atom or methoxy group, and R 3  represents a group selected from the groups of the general formulae (V), (VI), (VII), (VIII), (IX) and (X): ##STR3## in which X represents oxygen atom or vinylene group, R 5  represents allyl group, propargyl group, benzyl group, phenoxy group or 2,2-dichlorovinyloxy group, R 6  represents hydrogen atom, methyl group or halogen atom, R 7  represents hydrogen atom, cyano group, ethynyl group or trifluoromethyl group and m is an integer of 1-2, R 8  represents allyl group or alkadienyl group, Y represents oxygen atom or methylene group, R 9  represents hydrogen atom, methyl group, allyl group or halogen atom and R 10  represents methyl group or halogen atom.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel cyclopropane carboxylic acidester derivatives and the optical and geometrical isomers thereofexpressed by the general formula: ##STR4## wherein R₁ representshydrogen atom or methyl group, R₂ represents alkyl group, alkenyl group,haloalkyl group, haloalkenyl group having 1-6 carbon atoms and a groupselected from the groups of the general formulae (II), (III) and (IV):##STR5## in which n is an integer of 2-5, R₄ represents methyl group,chlorine atom or methoxy group, and R₃ represents a group selected fromthe groups of the general formulae (V), (VI), (VII), (VIII), (IX) and(X) ##STR6## in which X represents oxygen atom or vinylene group, R₅represents allyl group, propargyl group, benzyl group, phenoxy group or2,2-dichlorovinyloxy group, R₆ represents hydrogen atom, methyl group orhalogen atom, R₇ represents hydrogen atom, cyano group, ethynyl group ortrifluoromethyl group and m is an integer of 1-2, R₈ represents allylgroup or alkadienyl group, Y represents oxygen atom or methylene group,R₉ represents hydrogen atom, methyl group, allyl group or halogen atomand R₁₀ represents methyl group or halogen atom.

Further, the invention relates to the process for producing saidcyclopropane carboxylic acid ester derivatives or steric isomer thereofand to insecticides containing it as active ingredient.

Various alcohol components in chrysanthemumic acid esters have beenstudied and put into practical use. Such chrysanthemumic acid esters areliable to be decomposed by oxidation with light and therefore the usethereof in the open air has been limited. Recently, studies on acidcomponents in chrysanthemumic acid esters have been extensively made andthen compounds produced by substituting the methyl group by halogen atomwere found to be stable against light when compared to theconventionally used pyrethroid. However, taking the environmentalpollution and chronic toxicity into account, insecticides having thestructures similar to those of natural organic compounds consisting ofcarbon, hydrogen, oxygen and nitrogen will be advantageously used in thefuture. The present inventors have intensively investigated on theinsecticides and found out that the compounds expressed by theabovementioned formula (I) show remarkably strong insecticidal effectagainst various sanitary and agricultural pests, and that they are farmore stable against light than the conventional pyrethroids and showextremely low toxicity to warm blooded animals.

Thus, the compounds expressed by the formula (I) obviate the defect ofpyrethroids which are unstable to light, and are excellent insecticidehaving wide insecticidal spectrum and low toxicity. Furthermore, thecyclopropane carboxylic acids constituting the compounds of formula (I)are easily produced at a low price.

The present invention has been accomplished based on the knowledgementioned above. The compounds of the formula (I) used as activeingredient in the present invention can be produced according to theordinary processes for producing esters by reacting a carboxylic acid ora reactive derivative thereof having the general formula (XIII) ##STR7##wherein R₁ represents hydrogen atom or methyl group, R₂ represents alkylgroup, alkenyl group, haloalkyl group, haloalkenyl group having 1-6carbon atoms and a group selected from the groups of the generalformulae (II), (III) and (IV): ##STR8## in which n is an integer of 2-5,R₄ represents methyl group, chlorine atom or methoxy group, with analcohol or a reactive derivative thereof expressed by the formula (XIV):

    R.sub.3 -OH                                                (XIV)

wherein R₃ represents a group selected from the groups of the generalformulae (V), (VI), (VII), (VIII), (IX) and (X) ##STR9## in which Xrepresents oxygen atom or vinylene group, R₅ represents allyl group,propargyl group, benzyl group, phenoxy group or 2,2-dichlorovinyloxygroup, R₆ represents hydrogen atom, methyl group or halogen atom, R₇represents hydrogen atom, cyano group, ethynyl group or trifluoromethylgroup and m is an integer of 1-2, R₈ represents allyl group oralkadienyl group, Y represents oxygen atom or methylene group, R₉represents hydrogen atom, methyl group, allyl group or halogen atom andR₁₀ represents methyl group or halogen atom.

Reactive derivatives of carboxylic acid are, for example, acid halides,acid anhydrides, lower alkyl esters and alkali metal salts. Reactivederivative of alcohol is, for example, chloride. The reaction is carriedout in a suitable solvent in the presence of organic or inorganic base,or acid as deacidificating agent or catalyst, if desired, and atelevated temperature at need. Representative compounds of the formula(I) are shown in the following. As a matter of course, the compounds ofthe present invention are not limited only to the following ones.##STR10## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-isopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5204##STR11## 3'-phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-isobutoxycyclopropanecarboxylate n_(D) ²⁰ 1.5381 ##STR12## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-cyclohexylmethoxycyclopropane carboxylate n_(D) ²⁰ 1.5749##STR13## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5214##STR14## 3'-phenoxy-α'-cyanobenzyl 2,2,3-trimethyl-3-ethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5297 ##STR15## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-ethoxycyclopropane carboxylate n_(D) ²⁰ 1.5229 ##STR16##3'-phenoxybenzyl 2,2-dimethyl-3-n-propoxy cyclopropane carboxylate n_(D)²⁰ 1.5314 ##STR17## 3'-phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5386 ##STR18##3'-phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-n-amyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5470 ##STR19## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-n-hexyloxycyclopropane carboxylate n_(D) ²⁰ 1.5594##STR20## 5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-n-butoxycyclopropanecarboxylate n_(D) ²⁰ 1.5561 ##STR21## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5548##STR22## 5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-n-amyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5603 ##STR23## 5'-propargyl-2'-furylmethyl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5584##STR24## 2'-allyl-3'-methyl-2'-cyclopentene-1'-one-4'-yl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5570##STR25## 7'-methyl-2',3'-dihydrobenzofuran-3'-yl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5568##STR26## 3',4',5',6'-tetrahydrophthalimidemethyl2,2-dimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1,5451##STR27## 3'-(2,2-dichlorovinyloxy)-α'-cyanobenzyl2,2-dimethyl-3-isobutoxycyclopane carboxylate n_(D) ²⁰ 1.5587 ##STR28##5'-allyl-2'-methyl-3'-furylmethyl2,2-dimethyl-3-(3,3-dichloroallyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5622 ##STR29## 7'-allyl-indane-3'-yl2,2-dimethyl-3-(2,3-dibromo-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5704 ##STR30## 2',6'-dichloro-4'-propargyl-α'-ethynylbenzyl2,2-dimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5488 ##STR31##2'-(2,4-pentadienyl)-3'-methyl-2'-cyclopentene-1'-one-4'-yl2,2-dimethyl-3-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5603 ##STR32##3'-(2,2-dichlorovinyloxy)-α'-cyanobenzyl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5662##STR33## 4'-phenyl-3'-chloro-2'-butene-1'-yl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5578##STR34## 7'-methyl-2',3'-dihydrobenzofuran-3'-yl2,2-dimethyl-3-n-butoxy cyclopropanecarboxylate n_(D) ²⁰ 1.5527##STR35## 3'-(2,2-dichlorovinyloxy)-α'-cyanobenzyl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5600##STR36## 5'-propargyl-2'-furylmethyl2,2-dimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5474##STR37## 2'-allyl-3'-methyl-2'-cyclopentene-1'-one-4'-yl2,2-dimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5496##STR38## 3',4',5',6'-tetrahydrophthalimidemethyl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5546##STR39## 3'-benzyl-α'-cyanobenzyl2,2-dimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5826 ##STR40## 5'-propargyl-2'-methyl-3'-furylmethyl2,2-dimethyl-3-cyclopropoxy cyclopropane carboxylate n_(D) ²⁰ 1.5504##STR41## 7'-methyl-2',3'-dihydrobenzofuran-3'-yl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5615 ##STR42## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5326##STR43## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5473 ##STR44## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(1-methyl-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5423 ##STR45## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-isoamyloxycyclopropane carboxylate n_(D) ²⁰ 1.5469##STR46## 5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-n-propoxycyclopropanecarboxylate n_(D) ²⁰ 1.5502 ##STR47## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5671 ##STR48## 3'-phenoxybenzyl 2,2-dimethyl-3-isobutoxycyclopropanecarboxylate n_(D) ² 1.5327 ##STR49## 3'-phenoxybenzyl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5435 ##STR50## 3'-phenoxybenzyl2,2-dimethyl-3-cyclopentylmethoxycyclopropane carboxylate n_(D) ²⁰1.5471 ##STR51## 3'-phenoxybenzyl 2,2-dimethyl-3-n-amyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5439 ##STR52## 3'-phenoxybenzyl2,2-dimethyl-3-cyclopentyloxycyclopropane carboxylate n_(D) ²⁰ 1.5434##STR53## 3'-phenoxybenzyl 2,2-dimethyl-3-chloromethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5294 ##STR54## 3'-phenoxybenzyl2,2-dimethyl-3-isoamyloxycyclopropane carboxylate n_(D) ²⁰ 1.5401##STR55## 3'-phenoxybenzyl2,2-dimethyl-3-(2-chloro-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5483 ##STR56## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(3-bromo-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5606 ##STR57## 3'-phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-cyclobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5427 ##STR58##3'-phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-(2-chloroethoxy)-cyclopropanecarboxylate n_(D) ²⁰ 1.5451 ##STR59## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-ethoxycyclopropane carboxylate n_(D) ²⁰ 1.5450 ##STR60##5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-isopropoxycyclopropanecarboxylate n_(D) ²⁰ 1.5497 ##STR61## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5623 ##STR62## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-cyclobutylmethoxycyclopropane carboxylate n_(D) ²⁰ 1.5612##STR63## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-(2-chloroethoxy)-cyclopropane carboxylate n_(D) ²⁰ 1.5586##STR64## 3'-phenoxybenzyl 2,2-dimethyl-3-ethoxycyclopropane carboxylaten_(D) ²⁰ 1.5238 ##STR65## 3'-phenoxybenzyl2,2-dimethyl-3-isopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5288##STR66## 3'-phenoxybenzyl2,2-dimethyl-3-(1-methyl-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5346 ##STR67## 3'-phenoxybenzyl2,2-dimethyl-3-(3-methyl-2-butenyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5345 ##STR68## 3'-phenoxybenzyl 2,2-dimethyl-3-n-hexyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5493 ##STR69## 3'-phenoxybenzyl2,2-dimethyl-3-(3-chloro-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5406 ##STR70## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(3-methyl-2-butenyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5540 ##STR71## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-cyclopropylmethoxycyclopropane carboxylate n_(D) ²⁰1.5409 ##STR72## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(2-chloro-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5536 ##STR73## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-cyclopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5419##STR74## 3'-phenoxybenzyl 2,2-dimethyl-3-n-butoxycyclopropanecarboxylate n_(D) ²⁰ 1.5339 ##STR75## 3'-phenoxybenzyl2,2-dimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5275##STR76## 3'-phenoxybenzyl2,2-dimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5420 ##STR77## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5481 ##STR78## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5364##STR79## 3'-phenoxybenzyl 2,2-dimethyl-3-(2-chloroethoxy)-cyclopropanecarboxylate n_(D) ²⁰ 1.5394 ##STR80## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5463##STR81## 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-(1-methyl-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5542 ##STR82## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(2-methylallyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5422 ##STR83## 3'-phenoxybenzyl2,2-dimethyl-3-(2-chloroallyloxy)-cyclopropane carboxylate n_(D) ²⁰1.5360 ##STR84## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5377##STR85## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-i-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5422##STR86## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-(1-methyl-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5416 ##STR87## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5596 ##STR88## 3'-phenoxybenzyl2,2,3-trimethyl-3-cyclopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5327##STR89## 3'-phenoxybenzyl2,2,3-trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D)²⁰ 1.5480 ##STR90## 3'-Phenoxybenzyl2,2,3-trimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5432##STR91## 3'-phenoxybenzyl 2,2,3-trimethyl-3-n-amyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5401 ##STR92## 3'-phenoxybenzyl2,2,3-trimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5305##STR93## 3'-phenoxybenzyl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate n_(D) ²⁰ 1.5204 ##STR94## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5428##STR95## 5'-benzyl-3'-furylmethyl 2,2,3-trimethyl-3-ethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5471 ##STR96## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5512##STR97## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5519##STR98## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-(2-chloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5588 ##STR99## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-cyclopentylmethoxycyclopropane carboxylate n_(D) ²⁰1.5674 ##STR100## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-isopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5492##STR101## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5503##STR102## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D)²⁰ 1.5617 ##STR103## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-cyclohexyloxycyclopropane carboxylate n_(D) ²⁰ 1.5568##STR104## 3'-phenoxybenzyl2,2,3-trimethyl-3-(1-methyl-n-propoxy)-cyclopropan carboxylate n_(D) ²⁰1.5338 ##STR105## 3'-phenoxybenzyl2,2,3-trimethyl-3-chloromethoxycyclopropane carboxylate n_(D) ²⁰ 1.5288##STR106## 3'-phenoxybenzyl 2,2,3-trimethyl-3-isoamyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5446 ##STR107## 3'-phenoxybenzyl2,2,3-trimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5439 ##STR108## 3'-phenoxybenzyl2,2,3-trimethyl-3-cyclopentyloxycyclopropane carboxylate n_(D) ²⁰ 1.5498##STR109## 3'-phenoxybenzyl 2,2,3-trimethyl-3-ethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5264 ##STR110## 3'-phenoxybenzyl2,2,3-trimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5309##STR111## 3'-phenoxybenzyl 2,2,3-trimethyl-3-n-hexyloxycyclopropanecarboxylate n_(D) ²⁰ 1.5427 ##STR112## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-isoamyloxycyclopropane carboxylate n_(D) ²⁰ 1.5618##STR113## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-n-hexyloxycyclopropane carboxylate n_(D) ²⁰ 1.5597##STR114## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-(2-chloro-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5635 ##STR115## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-cyclobutylmethoxycyclopropane carboxylate n_(D) ²⁰1.5511 ##STR116## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-trifluoromethoxycyclopropane carboxylate n_(D) ²⁰1.5418 ##STR117## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-crotyloxycyclopropane carboxylate n_(D) ²⁰ 1,5580##STR118## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-(2-chloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5486 ##STR119## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5584##STR120## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5571##STR121## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate n_(D)²⁰ 1.5628 ##STR122## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5686##STR123## 5'-benzyl-3'-furylmethyl2,2,3-trimethyl-3-(2,2-dichloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5651 ##STR124## 3'-phenoxybenzyl2,2,3-trimethyl-3-isopropoxycyclopropane carboxylate n_(D) ²⁰ 1.5316##STR125## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5492##STR126## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5548##STR127## 3'-phenoxybenzyl2,2,3-trimethyl-3-(3-methyl-2-butenyloxy)-cyclopropane carboxylate n_(D)²⁰ 1.5416 ##STR128## 3'-phenoxybenzyl2,2,3-trimethyl-3-(2-chloroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5433 ##STR129## 3'-phenoxy-α'-cyanobenzyl2,2,3-trimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5408##STR130## 4'-phenoxy-2'-butyne-1'-yl2,2-dimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5386##STR131## 4'-phenyl-3'-methyl-2'-butene-1'-yl2,2-dimethyl-3-cyclopentylmethoxycyclopropane carboxylate n_(D) ²⁰1.5529 ##STR132## 5'-propargyl-2'-furylmethyl2,2,3-trimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5185##STR133## 3',4',5',6'-tetrahydrophthalimidemethyl2,2,3-trimethyl-3-ethoxycyclopropane carboxylate n_(D) ²⁰ 1.5390##STR134## 4'-phenoxy-2'-butyne-1'-yl2,2-dimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5341##STR135## 4'-allyl-α'-ethynylbenzyl2,2,3-trimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5376##STR136## 3',4',5',6'-tetrahydrophtalimidemethyl2,2-dimethyl-3-ethoxycyclopropane carboxylate n_(D) ²⁰ 1.5163 ##STR137##4'-phenoxy-2'-butyne-1'-yl 2,2,3-trimethyl-3-chloromethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5309 ##STR138##4'-phenyl-3'-chloro-2'-buten-1'-yl2,2-dimethyl-3-(3-chloro-n-propoxy)-cyclopropane carboxylate n_(D) ²⁰1.5572 ##STR139##2'-(2,4-pentadienyl)-3'-methyl-2'-cyclopenten-1'-one-4'-yl2,2-dimethyl-3-cyclopropylmethoxy cyclopropane carboxylate n_(D) ²⁰1.5540 ##STR140## 7'-chloro-indane-3'-yl2,2,3-trimethyl-3-allyloxycyclopropane carboxylate n_(D) ²⁰ 1.5539##STR141## 2'-methyl-4'-benzylbenzyl2,2-dimethyl-3-cyclopentyloxycyclopropane carboxylate n_(D) ²⁰ 1.5704##STR142## 5'-propargyl-2'-furylmethyl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5490##STR143## 2',3'-dihydrobenzofuran-3'-yl2,2-dimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5417##STR144## 5'-propargyl-2'-furylmethyl 2,2-dimethyl-3-ethoxycyclopropanecarboxylate n_(D) ²⁰ 1.5375 ##STR145## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(p-chlorophenoxy)-cyclopropane carboxylate n_(D) ²⁰1.5856 ##STR146## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(p-methylphenoxy)-cyclopropane carboxylate n_(D) ²⁰1.5817 ##STR147## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(p-methoxyphenoxy)-cyclopropane carboxylate n_(D) ²⁰1.5792 ##STR148## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-trifluoromethoxycyclopropane carboxylate n_(D) ²⁰ 1.5403##STR149## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-(2,2,2-trifluoroethoxy)-cyclopropane carboxylate n_(D) ²⁰1.5487 ##STR150## 3'-phenoxy-α'-trifluoromethylbenzyl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5390##STR151## 3'-phenoxy-α'-ethynylbenzyl2,2-dimethyl-3-n-propoxycyclopropane carboxylate n_(D) ²⁰ 1.5304##STR152## 3'-phenoxy-α'-trifluoromethylbenzyl2,2-dimethyl-3-isobutoxycyclopropane carboxylate n_(D) ²⁰ 1.5382##STR153## 3'-phenoxy-α'-ethynylbenzyl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5375##STR154## 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-difluoromethoxycyclopropane carboxylate n_(D) ²⁰ 1.5454##STR155## 2'-allyl-3'-methyl-2'-cyclopenten-1'-one-4'-yl2,2,3-trimethyl-3-methoxycyclopropane carboxylate n_(D) ²⁰ 1.5380##STR156## 3'-phenoxy-α'-trifluoromethylbenzyl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate n_(D) ²⁰ 1.5469##STR157## 4'-phenyl-3'-methyl-2'-buten-1'-yl2,2-dimethyl-3-n-butoxycyclopropane carboxylate n_(D) ²⁰ 1.5447

The process for producing the esters of the present invention will beexplained in more detail referring to the synthesis Examples.

EXAMPLE 1

5.1 g of 3-phenoxy-α-cyanobenzyl chloride is added into a solution of3.9 g of 2,2-dimethyl-3-cyclobutoxycyclopropane carboxylic aciddissolved in 50 ml of dimethylformamide, to which 4 ml of triethylamineis added with stirring. The reaction is carried out at 60°-80° C. for 3hours. The reaction mixture is dissolved in ether and the ether solutionis fully washed with diluted hydrochloric acid, aqueous solution ofsodium bicarbonate and aqueous solution of sodium chloride in order. Itis dried over sodium sulfate and thereafter ether is distilled off underreduced pressure to give 6.8 g of 3'-phenoxy-α'-cyanobenzyl2,2-dimethyl-3-cyclobutoxycyclopropane carboxylate.

EXAMPLE 2

3.1 g of 2,2-dimethyl-3-ethoxycyclopropane carboxylic acid and 3.7 g of3,4,5,6-tetrahydrophthalimide methylol are added into 50 ml of driedbenzen and 6.2 g of dicyclohexyl carbodiimide is added into thesolution. The solution is allowed to stand in a tightly stoppered vesselfor one night. The next day, the reaction is completed by heating underreflux for 4 hours. After cooling, precipitated dicyclohexylurea isfiltered off. Oily substance obtained by condensing the filtrate ispurified through a column of silica gel to obtain 4.5 g of3',4',5',6'-tetrahydrophthalimidemethyl2,2-dimethyl-3-ethoxycyclopropane carboxylate.

EXAMPLE 3

4.1 g of sodium 2,2,3-trimethyl-3-allyloxycyclopropane carboxylate and4.5 g of 3-phenoxybenzylchloride are dissolved into 50 ml of benzene.After reaction is carried out under reflux under a stream of nitrogenfor 3 hours, the reaction mixture is cooled. After filtering theprecipitated sodium chloride, the filtrate is thoroughly washed withaqueous solution of sodium chloride and dried over sodium sulfate.Benzene is distilled off under reduced pressure to give 6.8 g of3'-phenoxybenzyl 2,2,3-trimethyl-3-allyloxycyclopropane carboxylate.

EXAMPLE 4

4.4 g of 2,2-dimethyl-3-n-amyloxycyclopropane carboxylate acid chlorideis dissolved in 15 ml of dried benzene and a solution of 3.7 g of5-benzyl-3-furylmethylalcohol in 20 ml of dried benzene is added intothe solution. As a condensation accelerator, 3 ml of dried pyridine isadded into the solution to precipitate the crystals of pyridinehydrochloride. The reaction mixture thus prepared is allowed to stand ina tightly stoppered vessel at room temperature for one night. After thecrystals of pyridine hydrochloride are filtered off, the benzenesolution is dried over sodium sulfate. Thereafter benzene is distilledoff under reduced pressure to give 6.8 g of 5'-benzyl-3'-furylmethyl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate.

EXAMPLE 5

A mixture of 4.8 g of methyl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate and 3.3 gof 7-methyl-2,3-dihydrobenzofuran-3-ol is heated up to 150° C. When thetemperature reaches at 150° C., 0.25 g of sodium is added to the heatedsolution and methanol is started distilling off. When distillation ofmethanol ceases, another 0.25 g of sodium is added into the solution.The above-mentioned operation is repeated while keeping the temperatureat about 150° C. until theoretical quantity of methanol is obtained.Then, the mixture is cooled and dissolved in ether. The ether solutionis washed with diluted hydrochloric acid, aqueous solution of sodiumbicarbonate and aqueous solution of sodium chloride one after anotherand dried over sodium sulfate. Ether is distilled off under a reducedpressure to give 6.2 g of 7'-methyl-2',3'-dihydrobenzofuran-3'-yl2,2-dimethyl-3-(2,2-dichlorovinyloxy)-cyclopropane carboxylate.

EXAMPLE 6

8.2 g of 2,2-dimethyl-3-cyclopentylmethoxycyclopropane carboxylic acidanhydride and 3.2 g of 4-phenyl-3-methyl-2-butene-1-ol are dissolved in50 ml of dried pyridine and the solution is kept stirring at roomtemperature for one night. Next day, the reaction solution is pouredinto 100 g of ice water and the mixture is extracted three times with 20ml of ether. Three ether layers thus obtained are combined, which areextracted twice with 30 ml each of 5% aqueous solution of sodiumhydroxide to remove carboxylic acid by-produced. The ether layer iswashed with diluted hydrochloric acid, aqueous solution of sodiumbicarbonate and saturated solution of sodium chloride in order, andthereafter is dried over sodium sulfate. Ether is removed under reducedpressure to give a crude ester, which is purified through a column of 20g of active alumina to give 6.0 g of 4'-phenyl-3'-methyl-2'-butene-1'-yl2,2-dimethyl-3-cyclopentylmethoxycyclopropane carboxylate.

The compounds listed in the following table are prepared by the samemethod as in Examples 1-6. In the table 1, a, b, c, d, e in column ofesterification method mean as follows:

a. Esterification of salt of alkali metal, silver or organic tertiarybase of acid with halide of alcohol. (Example 1 and 3)

b. Dehydration-esterification of dicyclohexylcarboimide with an alcoholin an inert solvent. (Example 2)

c. Esterification through acid chloride (Example 4)

d. Transesterification in the presence of the catalyst of alkali metal,alkali metal alkoxide or sodium hydride. (Example 5)

e. Esterification through acid anhydride. (Example 6)

The representative compounds of the present invention will be shown inthe following table.

    TABLE 1            No.poundCom-      ##STR158##      R.sub.3 MethodficationEsteri- (%)Yield C,H,N,Ultimate analysis value                 1.      ##STR159##      ##STR160##      b 82 A:B: 71.43,71.79, 5.80,5.98, 4.023.99 C.sub.21 H.sub.21 NO.sub.4     2.      ##STR161##      ##STR162##      a 86 A:B: 73.41,73.28, 6.82,6.87, 3.503.56 C.sub.24 H.sub.27 NO.sub.4     4.      ##STR163##      ##STR164##      c 67 A:B: 72.36,72.33, 6.27,6.30, 3.853.84 C.sub.22 H.sub.23 NO.sub.4     5.      ##STR165##      ##STR166##      a 74 A:B: 72.67,72.82, 6.58,6.60, 3.703.69 C.sub.23 H.sub.25 NO.sub.4     6.      ##STR167##      ##STR168##      b 81 A:B: 72.50,72.33, 6.32, 6.30, 3.873.84 C.sub.22 H.sub.23 NO.sub.4     7.      ##STR169##      ##STR170##      a 90 A:B: 74.29,74.58, 7.38,7.34, ---- C.sub.22 H.sub.26 O.sub.4  8.      ##STR171##      ##STR172##      b 82 A:B: 73.16,73.28, 6.88,6.87, 3.583.56 C.sub.24 H.sub.27 NO.sub.4     9.      ##STR173##      ##STR174##      e 71 A:B: 73.65,73.71, 7.14,7.13, 3.463.44 C.sub.25 H.sub.29 NO.sub.4     11.      ##STR175##      ##STR176##      d 73 A:B: 74.19,74.16, 7.85,7.87, ---- C.sub.22 H.sub.28 O.sub.4  12.      ##STR177##      ##STR178##      c 70 A:B: 74.10,74.16, 7.89,7.87, ---- C.sub.22 H.sub.28 O.sub.4  14.      ##STR179##      ##STR180##      e 76 A:B: 71.76,71.70, 8.14,8.18, ---- C.sub.19 H.sub.26 O.sub.4  15.      ##STR181##      ##STR182##      c 68 A:B: 71.81,71.86, 8.99,8.98, ---- C.sub.20 H.sub.30 O.sub.4  16.      ##STR183##      ##STR184##      b 80 A:B: 72.22,72.29, 8.47,8.43, ---- C.sub.20 H.sub.28 O.sub.4  17.      ##STR185##      ##STR186##      d 72 A:B: 64.53,64.48, 7.42,7.46, 4.164.18 C.sub.18 H.sub.25 NO.sub.5     18.      ##STR187##      ##STR188##      a 81 A:B: 58.19,58.25, 5.60,5.58, 3.363.40 C.sub.20 H.sub.23 NO.sub.4     Cl      24.     ##STR189##      ##STR190##      c 74 A:B: 69.19,69.14, 7.93,7.96, ---- C.sub.21 H.sub.29 O.sub.3 Cl     25.      ##STR191##      ##STR192##      e 77 A:B: 71.76,71.70, 8.16,8.18, ---- C.sub.19 H.sub.26 O.sub.4  27.      ##STR193##      ##STR194##      b 75 A:B: 70.19,70.34, 7.63,7.59, ---- C.sub.17 H.sub.22 O.sub.4  28.      ##STR195##      ##STR196##      d 76 A:B: 71.30,71.25, 8.70,8.75, ---- C.sub.19 H.sub.28 O.sub.4  29.      ##STR197##      ##STR198##      c 68 A:B: 65.38,65.33, 7.70,7.74, 4.024.01 C.sub.19 H.sub.27 NO.sub. 5     31.      ##STR199##      ##STR200##      d 70 A:B: 71.55,71.52, 7.25,7.28, ---- C.sub.18 H.sub.22 O.sub.4  34.      ##STR201##      ##STR202##      b 79 A:B: 61.07,61.11, 4.86,4.84, 3.243.23 C.sub.22 H.sub.21 NO.sub.4     Cl.sub.2      41.     ##STR203##      ##STR204##      a 78 A:B: 76.09,76.14, 7.63,7.61, ---- C.sub. 25 H.sub.30 O.sub.4  52.      ##STR205##      ##STR206##      b 76 A:B: 60.71,60.76, 5.10,5.06, ---- C.sub.20 H.sub.20 O.sub.4     Cl.sub.2      61.     ##STR207##      ##STR208##      a 81 A:B: 74.10,74.07, 6.64,6.67, 3.443.46 C.sub.25 H.sub.27 NO.sub.4     89.      ##STR209##      ##STR210##      e 72 A:B: 66.90,66.93, 6.66,6.64,  ---- C.sub.21 H.sub.25 O.sub.4 Cl     94.      ##STR211##      ##STR212##      c 69 A:B: 74.70,74.83, 7.20,7.16, 3.24,3.23 C.sub.27 H.sub.31 NO.sub.4     121.      ##STR213##      ##STR214##      d 65 A:B: 72.11,72.15, 7.63,7.59, ---- C.sub.19 H.sub.24 O.sub.4  126.      ##STR215##      ##STR216##      b 74 A:B: 76.88, 76.92, 7.71,7.69, ---- C.sub.20 H.sub.24 O.sub.3  129.      ##STR217##      ##STR218##      a 78 A:B: 61.42,61.46, 6.49,6.47, ---- C.sub.19 H.sub.24 O.sub.3     Cl.sub.2      130.     ##STR219##      ##STR220##      a 83 A:B: 73.29,73.26, 8.13,8.14, ---- C.sub.21 H.sub.28 O.sub.4  131.      ##STR221##      ##STR222##      c 67 A:B: 68.22,68.16, 6.85,6.88, -- -- C.sub.19 H.sub.23 O.sub.3 Cl     132.      ##STR223##      ##STR224##      a 82 A:B: 79.46,79.59, 8.19,8.16, ---- C.sub.26 H.sub.32     Note:     A; Experimental result     B; Calculated value

2,2-dimethyl-3-alkoxycyclopropane carboxylic acid and2,2,3-trimethyl-3-alkoxycyclopropane carboxylic acid constituting thecompounds of the present invention can be easily prepared by using theethers produced by the methods described in Bull. Soc. Chim., France,1966 (2), 734 and J. Chem. Soc., 5225 (1965) and the substitutedacrylates produced by the method described in Arch. Pharm. 287, 129(1954) as starting material, for instance, as shown in Steps 1 and 2.##STR225##

EXAMPLE 7

28 g of n-amyl-1-isobutenyl ether and 1 g of copper sulfate are placedin a 300 ml three necked flask and then 0.5 g of ethyl diazoacetate isadded thereto. The mixture is heated at about 120° C. and when nitrogengas is continuously generated and the reaction starts, 11 g of ethyldiazoacetate is gradually dropped into the reaction mixture whilekeeping temperature at around 120° C. After the reaction is completed,the reaction mixture is filtered and the filtrate is distilled underreduced pressure to give 16.5 g of ethyl2,2-dimethyl-3-n-amyloxycyclopropane carboxylate (b.p. 133°-137° C./20mmHg). 100 ml of 2 N methanol solution of sodium hydroxide is added intothe reaction product, which is heated under reflux for 30 minutes.Subsequently, methanol is removed under reduced pressure and water isadded into the mixture. Adding concentrated hydrochloric acid, themixture is made acidic and then extracted three times with 50 ml ofchloroform.

The three chloroform layers are combined and dried over anhydrous sodiumsulfate. Then chloroform is distilled off under reduced pressure to give14.5 g of 2,2-dimethyl-3-n-amyloxycyclopropane carboxylic acid.

EXAMPLE 8

A newly prepared ether solution of about 7 g of dimethyl diazomethane iscooled to -50°˜-70° C. with dry ice-acetone. A solution of 15.0 g ofethyl 3-methoxycrotonate dissolved in 100 ml of ether is droppedgradually into the cooled ether solution. After finished dropping, thereaction liquid is kept at this temperature for three hours and then isallowed to stand at room temperature until the colour ofdimethyldiazomethane disappears. Thereafter ether is distilled off togive 20 g of the oily matter of4-methoxy-4,5,5-trimethyl-1-pyrazoline-3-carboxylate. The pyrazolineester is gradually heated up to 140° C. under reflux and it is kept at160° C. for 30 minutes after creasing the boiling. After cooling, wateris added into the reaction mixture and the mixture is extracted withether. Ether is distilled off under reduced pressure to yield 16.2 g ofethyl 2,2,3-trimethyl-3-methoxycyclopropane carboxylic acid (b.p.122°-126° C./20 mmHg). The product is dissolved in 100 ml of methanoland 20 ml of 40% aqueous solution of sodium hydroxide is added into thesolution. The solution is heated under reflux for 1 hour. Methanol isdistilled off under reduced pressure and the residue is diluted with 60ml of water, acidified with hydrochloric acid and extracted three timeswith 50 ml each of chloroform. The chloroform layers are combined, whichis dried over anhydrous sodium sulfate and chloroform is distilled offunder reduced pressure to give 14.5 g of 2,2,3-trimethyl-3-methoxycyclopropane carboxylic acid.

The compounds of the present invention which are novel one are solid orliquid at room temperature and usually easily soluble in organicsolvent. Accordingly, they may be used as ingredients in insecticidalsprays in the form of emulsion, solution, powder, wettable powder andaerosol, etc. In addition, they may be used as insecticides forfumigation by mixing them with some appropriate substrate such aspowdered wood and making mosquito incense sticks. Furthermore, thesecompounds show also strong effect as mosquito incense sticks when theyare employed as insecticides for heating and evaporating use. Namely,they are dissolved in a suitable organic solvent and the solution isabsorbed into a carrier and then the resulting product is heated on anappropriate heater. The compounds of the present invention are morestable to light than the conventional chrysanthemum monocarboxylate andthey have wide insecticidal spectrum and exhibit excellent effectagainst the insect pests which is now resistant to organic phosphorousinsecticides and carbamate insecticides. In addition as they are lowtoxic and at low cost, they may be used as agricultural insecticideswhich are replaceable with conventionally used the organic phosphorousinsecticides and the organic chlorine insecticides.

Addition of some synergists into the compounds, for example,N-octylbicycloheptene dicarboxyimide (MGK-264 is the commercial name), amixture composed of N-octylbicycloheptene dicarboxyimide andarylsulfonic acid salt (MGK-5026 is the commercial name),n-octyl-1-isopropyl-4-methylbicyclo-[2,2,2,]oct-5-en-2,3-dicarboxyimide,octachlorodipropylether, or piperonylbutoxide, can enhance theinsecticidal effect.

The compositions for various purposes can be prepared by mixing thecompounds of the present invention with other insecticides, say, theorganic phosphorous insecticide such as fenitrothion, DDVP(dichlorvos)and diazinon; carbamate insecticide such as1-naphthyl-N-methylcarbamate, 3,4-dimethyl phenyl-N-methylcarbamate;conventionally used pyrethroid insecticides such as pyrethrin,allethrin, phthalthrin, furamethrin, phenothrin, permethrin,cypermethrin, decamethrin, fenvalerate and fenpropanate; theinsecticides such as cartap, chlorphenamidine, methomyl or acaricidemiticide, germicide, nematocide, herbicide, plant growth regulator,fertilizer and other agrochemicals.

Therefore reduction of labor and the synergistic effects, for exampleexcellent effect against pests which are resistant to the organicphosphorus and carbamate insecticide, can be highly expected. In orderto show the excellent effect of the compounds of the present invention,the test results on light stability and insecticidal effect of thecompounds are given in the following.

TEST EXAMPLE 1

About 50 mg each of 10 compounds selected from the above-shown compoundsof the present invention and conventionally used pyrethroid is thinlyspread on the bottom of a glass vessel having a diameter of 3 cm. Eachcompound in the vessel is exposed to sun light outdoors on a sunny dayin summer from 9 A.M. to 5 P.M. After a given period of time elapsed,each compound is taken into a vessel with 50 ml of acetone andconcentrated. Residual ratio (%) of the compounds is determined by meansof a gas chromatography. The numbers of the tested compounds correspondto those of the compounds of the formula (I) mentioned above.

                  TABLE 2                                                         ______________________________________                                        One day     Two day  Three day Four day                                                                             Five day                                Exposure    Exposure Exposure  Exposure                                                                             Exposure                                ______________________________________                                        Allethrin                                                                            43       22        4      --     --                                    Resme- 88       40        8      --     --                                    thrin                                                                         Pheno- 92       72       54      27      5                                    thrin                                                                         2.     95       94       88      82     75                                    4.     92       86       81      79     73                                    8.     93       89       80      74     70                                    13.    92       87       79      68     50                                    16.    94       89       82      77     69                                    18.    95       88       83      79     71                                    24.    95       88       80      75     58                                    28.    93       85       76      57     34                                    47.    97       93       86      82     76                                    132.   96       90       84      80     75                                    ______________________________________                                    

As is obvious from the above results, the compounds of the presentinvention are far more stable against sun light than conventionally usedpyrethroid. This means that when the compounds of the present inventionare used outdoors, they are expected to exhibit an excellent andpersistent effect.

TEST EXAMPLE 2

Insecticidal effect by spraying test

With respect to each 0.2% kerosene solution of 148 compounds of thepresent invention which are exemplified above (A), a kerosene solutioncontaining 0.2% of each compound of the present invention and 0.8% ofpiperonylbutoxide (B), a kerosene solution containing 0.1% of eachcompound of the present invention and 0.1% of phthalthrin (C), a 0.2%kerosene solution of allethrin and a 0.2% kerosene solution ofphthalthrin, the relative effect values are estimated from theknock-down rate of house flies by spraying and the mortality after 24hours is obtained as follows:

                  TABLE 3                                                         ______________________________________                                        Compound      (A)        (B)        (C)                                       ______________________________________                                        Allethrin   1.00 (26)    --         --                                        Phthalthrin 2.15 (34)    --         --                                        1.          1.58 (100) 1.84 (100) 1.79 (100)                                  2.          1.70 (100) 1.92 (100) 1.93 (100)                                  3.          1.41 (95)  1.75 (100) 1.82 (98)                                   4.          1.92 (100) 2.24 (100) 2.18 (100)                                  5.          1.74 (100) 1.95 (100) 1.96 (100)                                  6.          2.09 (100) 2.70 (100) 2.51 (100)                                  7.          1.81 (100) 2.32 (100) 2.10 (100)                                  8.          1.85 (100) 2.17 (100) 2.04 (100)                                  9.          1.97 (100) 2.36 (100) 2.12 (100)                                  10.         1.83 (100) 2.29 (100) 2.04 (100)                                  11.         2.54 (100) 3.03 (100) 2.84 (100)                                  12.         2.51 (100) 2.95 (100) 2.74 (100)                                  13.         3.28 (100) 3.84 (100) 3.02 (100)                                  14.         2.91 (100) 3.48 (100) 3.15 (100)                                  15.         2.75 (100) 3.26 (100) 2.94 (100)                                  16.         2.54 (100) 2.90 (100) 2.69 (100)                                  17.         3.06 (100) 3.72 (100) 3.16 (100)                                  18.         2.14 (100) 2.53 (100) 2.24 (100)                                  19.         2.28 (100) 2.64 (100) 2.37 (100)                                  20.         1.82 (100) 2.29 (100) 2.18 (100)                                  21.         1.33 (80)  1.83 (98)  1.86 (85)                                   22.         2.16 (100) 2.57 (100) 2.48 (100)                                  23.         2.05 (100) 2.65 (100) 2.36 (100)                                  24.         1.96 (100) 2.25 (100) 2.17 (100)                                  25.         2.32 (100) 2.77 (100) 2.58 (100)                                  26.         2.09 (100) 2.49 (100) 2.50 (100)                                  27.         2.28 (100) 2.61 (100) 2.58 (100)                                  28.         2.28 (100) 2.57 (100) 2.50 (100)                                  29.         2.40 (100) 2.86 (100) 2.78 (100)                                  30.         1.72 (100) 2.11 (100) 2.05 (100)                                  31.         1.63 (95)  1.93 (100) 1.81 (100)                                  32.         1.94 (100) 2.29 (100) 2.17 (100)                                  33.         2.47 (100) 2.37 (100) 2.51 (100)                                  34.         2.30 (100) 2.66 (100) 2.40 (100)                                  35.         1.64 (92)  2.14 (100) 2.18 (100)                                  36.         1.54 (90)  1.88 (100) 1.91 (95)                                   37.         2.39 (100) 2.90 (100) 2.77 (100)                                  38.         2.50 (100) 2.84 (100) 2.23 (100)                                  39.         1.92 (95)  2.35 (100) 2.19 (100)                                  40.         2.03 (100) 2.46 (100) 2.24 (100)                                  41.         1.73 (90)  2.12 (100) 2.15 (98)                                   42.         1.80 (95)  2.09 (100) 1.97 (100)                                  43.         1.77 (90)  1.93 (100) 2.04 (90)                                   44.         1.81 (100) 2.07 (100) 2.08 (100)                                  45.         1.44 (85)  1.91 (98)  1.83 (88)                                   46.         1.79 (90)  2.03 (100) 2.11 (100)                                  47.         1.82 (100) 2.19 (100) 2.06 (100)                                  48.         1.91 (100) 2.33 (100) 2.17 (100)                                  49.         2.16 (100) 2.40 (100) 2.23 (100)                                  50.         2.14 (100) 2.58 (100) 2.42 (100)                                  51.         1.97 (100) 2.35 (100) 2.11 (92)                                   52.         2.20 (100) 2.64 (100) 2.39 (100)                                  53.         1.88 (95)  2.20 (100) 2.07 (100)                                  54.         1.91 (100) 2.18 (100) 2.20 (100)                                  55.         1.80 (90)  2.05 (100) 2.09 (100)                                  56.         1.76 (85)  1.90 (100) 2.02 (92)                                   57.         1.71 (82)  1.96 (98)  1.94 (90)                                   58.         1.38 (78)  1.81 (90)  1.88 (80)                                   59.         1.40 (80)  1.85 (90)  1.79 (76)                                   60.         1.65 (84)  2.01 (98)  1.97 (90)                                   61.         1.98 (100) 2.30 (100) 2.15 (100)                                  62.         2.05 (100) 2.42 (100) 2.16 (100)                                  63.         1.95 (98)  2.17 (100) 2.02 (100)                                  64.         1.93 (100) 2.14 (100) 2.02 (100)                                  65.         1.70 (70)  1.98 (100) 2.03 (100)                                  66.         1 45 (78)  1.88 (92)  1.90 (85)                                   67.         1.71 (85)  2.02 (100) 2.05 (95)                                   68.         2.19 (100) 2.54 (100) 2.44 (100)                                  69.         1.94 (100) 2.36 (100) 2.17 (100)                                  70.         1.83 (90)  2.09 (100) 2.11 (100)                                  71.         1.92 (98)  2.20 (100) 2.04 (100)                                  72.         1.83 (95)  2.04 (100) 2.02 (100)                                  73.         1.97 (100) 2.34 (100) 2.21 (100)                                  74.         1.52 (80)  1.86 (95)  1.90 (85)                                   75.         1.98 (100) 2.27 (100) 2.18 (100)                                  76.         1.69 (86)  1.94 (100) 1.90 (92)                                   77.         1.58 (82)  1.90 (95)  1.88 (90)                                   78.         1.66 (90)  2.02 (100) 1.98 (95)                                   79.         1.80 (95)  2.15 (100) 2.10 (100)                                  80.         1.76 (80)  2.04 (98)  1.98 (85)                                   81.         1.36 (78)  1.80 (90)  1.85 (82)                                   82.         1.25 (80)  1.61 (90)  2.03 (90)                                   83.         1.40 (82)  1.84 (95)  1.83 (90)                                   84.         1.85 (100) 2.07 (100) 2.08 (100)                                  85.         1.50 (85)  1.79 (95)  1.93 (95)                                   86.         1.21 (80)  1.40 (90)  1.81 (85)                                   87.         1.27 (75)  1.51 (90)  1.76 (85)                                   88.         1.31 (80)  1.51 (90)  1.95 (90)                                   89.         1.26 (80)  1.53 (95)  1.83 (90)                                   90.         1.15 (80)  1.37 (95)  1.76 (90)                                   91.         1.54 (80)  1.79 (90)  2.07 (95)                                   92.         1.73 (90)  2.01 (100) 2.07 (100)                                  93.         1.39 (80)  1.60 (95)  1.94 (90)                                   94.         1.09 (80)  1.21 (95)  1.83 (90)                                   95.         1.76 (85)  1.90 (100) 2.02 (92)                                   96.         1.71 (82)  1.96 (98)  1.94 (90)                                   97.         1.93 (98)  2.28 (100) 2.26 (100)                                  98.         1.88 (95)  2.36 (100) 2.13 (100)                                  99.         1.41 (70)  1.75 (90)  1.93 (90)                                   100.        1.74 (90)  2.05 (100) 2.02 (100)                                  101.        1.82 (90)  2.11 (100) 2.08 (95)                                   102.        1.50 (80)  1.71 (90)  1.93 (90)                                   103.        1.59 (80)  1.85 (90)  2.07 (95)                                   104.        1.80 (90)  1.93 (100) 2.11 (100)                                  105.        1.50 (80)  1.71 (95)  2.04 (90)                                   106.        1.79 (85)  1.94 (100) 1.99 (90)                                   107.        1.81 (90)  2.01 (100) 2.10 (100)                                  108.        1.70 (80)  1.96 (100) 2.03 (100)                                  109.        1.68 (80)  1.89 (100) 2.11 (95)                                   110.        1.45 (75)  1.84 (90)  1.86 (85)                                   111.        1.54 (80)  1.70 (95)  1.89 (90)                                   112.        1.35 (75)  1.81 (90)  1.93 (80)                                   113.        1.47 (90)  1.69 (100) 1.95 (95)                                   114.        1.56 (100) 1.81 (100) 2.03 (100)                                  115.        1.49 (80)  1.71 (95)  1.96 (100)                                  116.        1.94 (100) 2.33 (100) 2.20 (100)                                  117.        1.86 (100) 2.04 (100) 2.07 (100)                                  118.        1.63 (85)  1.87 (95)  2.01 (100)                                  119.        1.47 (85)  1.71 (100) 1.89 (95)                                   120.        1.80 (95)  2.15 (100) 2.08 (100)                                  121.        1.52 (90)  1.91 (100) 1.84 (87)                                   122.        1.64 (97)  2.03 (100) 1.97 (90)                                   123.        1.85 (80)  2.19 (100) 2.13 (80)                                   124.        1.51 (72)  1.98 (95)  1.95 (77)                                   125.        1.36 (71)  1.86 (90)  1.79 (68)                                   126.        1.49 (82)  2.05 (100) 1.90 (85)                                   127.        1.77 (88)  2.12 (100) 2.04 (89)                                   128.        1.38 (75)  1.90 (98)  1.88 (74)                                   129.        1.60 (100) 2.24 (100) 2.17 (100)                                  130.        1.39 (75)  1.91 (95)  1.76 (78)                                   131.        1.24 (68)  1.87 (90)  1.78 (74)                                   132.        1.82 (100) 2.24 (100) 2.03 (100)                                  133.        2.09 (100) 2.48 (100) 2.27 (100)                                  134.        2.36 (100) 2.75 (100) 2.62 (100)                                  135.        1.98 (100) 2.41 (100) 2.25 (100)                                  136.        1.86 (100) 2.20 (100) 2.11 (100)                                  137.        1.82 (100) 2.16 (100) 2.05 (100)                                  138.        1.81 (100) 2.17 (100) 2.13 (100)                                  139.        1.75 (90)  2.04 (100) 1.97 (98)                                   140.        1.90 (100) 2.23 (100) 2.06 (100)                                  141.        2.01 (100) 2.56 (100) 2.49 (100)                                  142.        1.79 (100) 2.11 (100) 2.10 (100)                                  143.        1.98 (100) 2.24 (100) 2.15 (100)                                  144.        1.83 (95)  2.19 (100) 2.14 (100)                                  145.        1.92 (100) 2.25 (100) 2.23 (100)                                  146.        1.77 (95)  2.08 (100) 2.02 (100)                                  147.        2.04 (100) 2.38 (100) 2.26 (100)                                  148.        1.80 (98)  2.12 (100) 2.08 (100)                                  ______________________________________                                    

As is seen from the above-shown test results, when 0.2% kerosenesolution of each compound of the present invention is singly employed,each shows better knock-down effect than allethrin of pyrethroidconventionally used and the mortality rate of nearly 100%.

In case when piperonylbutoxide is added as synergyst, the knock-down andmortality effects are further enhanced. And also the solution of eachcompound of the present invention mixed with phthalthrin displays thesynergystic effect on knock-down and mortality effects.

TEST EXAMPLE 3

Insecticidal effect by fumigation test

Mosquito incense sticks containing each 0.5% active ingredient wereprepared and tested for the knock-down rate of mosquitoes (Culex PipiensPallens). These test were carried out in accordance with the proceduredescribed by Nagasawa, Katsuda and others in "Bochu-Kagaku" Vol. 16,page 176 (1951). The relative effect values of these mosquito incensesticks are as follows:

                  TABLE 4                                                         ______________________________________                                        Compound  Probit 4     Probit 5 Probit 6                                      ______________________________________                                        Allethrin 1.00         1.00     1.00                                          1.        1.37         1.40     1.43                                          2.        1.51         1.56     1.59                                          3.        1.25         1.28     1.31                                          4.        1.70         1.74     1.79                                          5.        1.52         1.55     1.58                                          7.        1.60         1.63     1.66                                          8.        1.62         1.65     1.69                                          9.        1.65         1.68     1.71                                          11.       1.81         1.85     1.88                                          13.       1.92         1.97     2.03                                          14.       2.46         2.50     2.54                                          15.       2.13         2.16     2.20                                          16.       1.71         1.75     1.79                                          17.       1.84         1.86     1.89                                          18.       1.56         1.59     1.61                                          19.       2.01         2.06     2.09                                          20.       1.75         1.78     1.80                                          22.       2.19         2.22     2.26                                          24.       1.70         1.74     1.78                                          25.       1.68         1.72     1.76                                          27.       2.25         2.31     2.37                                          28.       2.10         2.13     2.18                                          29.       1.84         1.86     1.90                                          31.       1.96         1.99     2.04                                          32.       1.70         1.73     1.76                                          33.       1.64         1.68     1.70                                          34.       1.60         1.63     1.68                                          35.       1.41         1.45     1.47                                          36.       1.32         1.33     1.37                                          38.       1.50         1.51     1.54                                          41.       1.45         1.49     1.53                                          45.       1.19         1.21     1.24                                          49.       1.57         1.61     1.63                                          52.       1.49         1.53     1.57                                          54.       1.34         1.39     1.42                                          58.       1.16         1.18     1.22                                          67.       1.33         1.37     1.41                                          68.       1.56         1.59     1.62                                          70.       1.45         1.48     1.52                                          73.       1.56         1.58     1.61                                          74.       1.31         1.35     1.38                                          75.       1.49         1.53     1.56                                          78.       1.27         1.30     1.35                                          79.       1.11         1.14     1.20                                          82.       1.23         1.29     1.33                                          84.       1.28         1.30     1.34                                          85.       1.28         1.33     1.37                                          87.       1.37         1.41     1.46                                          90.       1.09         1.15     1.24                                          92.       1.40         1.44     1.47                                          93.       1.25         1.31     1.34                                          96.       1.20         1.23     1.29                                          101.      1.46         1.49     1.53                                          103.      1.29         1.34     1.40                                          106.      1.22         1.28     1.30                                          108.      1.20         1.25     1.28                                          111.      1.36         1.40     1.45                                          114.      1.33         1.36     1.40                                          116.      1.48         1.50     1.54                                          118.      1.20         1.21     1.28                                          120.      1.31         1.35     1.38                                          124.      1.37         1.40     1.42                                          127.      1.43         1.47     1.50                                          130.      1.19         1.23     1.26                                          135.      1.56         1.60     1.63                                          136.      1.69         1.71     1.75                                          137.      1.68         1.71     1.74                                          141.      1.52         1.55     1.58                                          146.      1.49         1.52     1.56                                          ______________________________________                                    

In the table 4, the knock-down ratios of the mosquitoes in Probit 4, 5and 6 are 16%, 50% and 84% respectivelly and the relative activity iscalculated from the time required for attaining said knock-down rates.From the above results, it can be seen that the compounds of the presentinvention show the more excellent effect than allethrin and they can bealso used as an active ingredient of a fumigant.

TEST EXAMPLE 4

Insecticidal test by topical application method

Acetone solutions each containing a given amount of allethrin and eachcompound of the present invention, and those containing said activeingredients together with piperonyl butoxide twice the quantity of theactive ingredient are prepared. Each solution is applied to the breastand the back of house fly by means of microsyringe. Relative mortalityof the compounds in comparison with allethrin and the synergistic effectby piperonyl butoxide are examined based on the mortality at 24 hrs.after the application. The result is indicated in the table below.

                  TABLE 5                                                         ______________________________________                                                               Relative                                                                      mortality                                                                     when     Rate of                                                 Relative     synergist                                                                              enhanced                                      Compound  mortality    added    mortality                                     ______________________________________                                        Allethrin 1.00         2.35     2.4                                           1.        4.76         17.14    3.6                                           2.        6.80         22.44    3.3                                           4.        5.52         22.08    4.0                                           6.        5.96         26.82    4.5                                           8.        4.52         17.18    3.8                                           9.        7.13         29.23    4.1                                           10.       5.35         22.47    4.2                                           11.       8.76         31.54    3.6                                           13.       9.26         33.34    3.6                                           14.       5.34         21.89    4.1                                           15.       4.81         14.43    3.0                                           16.       6.53         24.16    3.7                                           17.       3.90         13.26    3.4                                           18.       6.47         27.17    4.2                                           20.       5.65         19.78    3.5                                           22        4.62         13.40    2.9                                           24.       7.02         23.87    3.4                                           30.       4.49         17.96    4.0                                           33.       6.38         22.33    3.5                                           34.       6.14         19.65    3.2                                           40.       5.33         20.79    3.9                                           61.       5.91         21.87    3.7                                           65.       3.77         14.70    3.9                                           68.       6.04         24.16    4.0 - 75. 4.62 17.56 3.8                      80.       3.54         11.68    3.3                                           84.       4.82         17.83    3.7                                           90.       4.13         16.11    3.9                                           94.       3.76         13.54    3.6                                           103.      4.05         14.99    3.7                                           106.      5.11         16.86    3.3                                           111.      5.74         22.96    4.0                                           114.      4.54         16.34    3.6                                           120.      4.83         18.35    3.8                                           123.      4.50         14.85    3.3                                           128.      3.49         14.66    4.2                                           132.      5.71         19.99    3.5                                           139.      4.43         15.06    3.4                                           146.      5.05         18.18    3.6                                           ______________________________________                                    

Addition of piperonyl butoxide enhances the insecticidal effect of thecompounds of the present invention more than 3 times as high. This meansthat high mortality can be attained by a smaller amount of the compoundsof the present invention.

REFERENCE EXAMPLE 1

Each 0.2 parts of Compounds (1), (4), (8), (13), (33) and (75) of thepresent invention is dissolved in sufficient kerosene to form 100 partsof 0.2% solution.

REFERENCE EXAMPLE 2

Each 0.2 parts of Compounds (2), (5), (9), (14), (34) and (76) of thepresent invention and 0.8 parts of piperonylbutoxide are dissolved insufficient kerosene to form 100 parts of solution.

REFERENCE EXAMPLE 3

Each 20 parts of Compounds (16), (36), (78) and (136) of the presentinvention, 10 parts of Solpol SM-200 (tradename of Toho Chemical Co.)and 70 parts of xylene are mixed with stirring to form 20% emulsifiableconcentrate.

REFERENCE EXAMPLE 4

Each 0.4 parts of Compounds (19), (42) and (84) of the presentinvention, 0.1 part of resmethrin and 1.5 parts of octachlorodipropylether are dissolved in 28 parts of rectified kerosene. The solution ischarged in an aerosol vessel and a jet-valve is attached to the vessel,through which 70 parts of propellant (liquefied petroleum gas) arecompressed into the vessel to obtain an aerosol preparation.

REFERENCE EXAMPLE 5

Each 0.5 g of Compounds (7), (22), (51) and (93) of the presentinvention and 0.5 g of BHT are uniformly mixed with 99.0 g of substratefor mosquito incense sticks such as pyrethrum extract powder, powderedwood and starch, etc. The resulting substance is molded into mosquitoincense stick by a publicly known process.

REFERENCE EXAMPLE 6

Each 0.4 g of Compounds (59) and (101) of the present invention and 1.0g of MGK-5026 are uniformly blended with 98.6 g of substrate formosquito incense stick. The resulting substance is molded into mosquitoincense stick by a publicly known process.

REFERENCE EXAMPLE 7

Each 3 parts of Compounds (10), (25), (67) and (116) of the presentinvention and 97 parts of clay are blended well and pulverized to obtain3% powder.

REFERENCE EXAMPLE 8

Each 40 parts of Compounds (6), (74) and (104) of the present invention,35 parts of diatomaceous earth, 20 parts of clay, 3 parts oflaurylsulfonic acid salt and 2 parts of carboxymethylcellulose arecrushed and blended to form wettable powder.

TEST EXAMPLE 4

Each emulsifiable concentrate containing Compounds (2), (5), (8), (13),(14), (16), (26), (32), (35), (36), (39), (48), (53), (57), (62), (66),(69), (73), (77), (78), (81), (90), (95), (99), (104), (108), (115),(117), (119), (123), (128), (132), (136), and (141) of the presentinvention, which are prepared by the method mentioned in ReferenceExample 3, is diluted with water to prepare 1/1000 solution. 100 l/10aof the solution is sprayed onto Japanese radish leaves at the 5-6 leafstage, on which a lot of green peach aphid (Myzus persicae Sulzer) aregrown all over the surface. After 2 days, the green peach aphidesdecrease to less than 1/10 in each case when compared to those beforespraying.

TEST EXAMPLE 5

One day before applying insecticide, about 200 aphides (Aphis craccivoraKoch) are put on each broad bean plant (Vicia faba L) in a pot. Eachwettable powder containing Compounds (1), (4), (6), (7), (14), (17),(18), (30), (34), (38), (46), (51), (56), (59), (67), (70), (74), (76),(80), (88), (93), (98), (101), (104), (109), (112), (117), (120), (124),(127), (130), (133), (138) and (144) of the present invention, which areprepared by the method of Reference Example 8 is diluted with water toprepare 1/4000 solution. Each 10 ml/pot of the diluted solution issprayed on the bean leaves which swarm with aphides by means ofcompressed air spray. After two days, any increase of damage is notobserved in each case.

TEST EXAMPLE 6

Each emulsifiable concentrate containing Compounds (1), (3), (4), (8),(9), (10), (12), (13), (15), (16), (21), (23), (33), (36), (44), (49),(55), (57), (64), (71), (73) (75), (78), (85), (91), (97), (100), (106),(113), (115), (119), (126), (134), (136), (137), (143), and (147) of thepresent invention, which is prepared by the method in Reference Example3, is diluted with water to prepare 1/2000 solution. Cabbage leaves areimmersed in the solution for about five seconds. After the coating isdried, the leaves are put in a glass vessel in which 10 sound larvae ofcabbage armyworm are settled. The larvae are supplied twice at the datewhen the test leaves are prepared and 5 days after that date. Mortalityof Compounds tested after 24 hrs. is listed as follows:

                  TABLE 6                                                         ______________________________________                                        Compound       First day 5th day                                              ______________________________________                                        Salithion      40     (%)    5       (%)                                      1.             85            70                                               3.             85            75                                               4.             85            70                                               8.             100           100                                              9.             100           100                                              10.            100           100                                              12.            100           80                                               13.            100           85                                               15.            100           80                                               16.            100           100                                              21.            95            80                                               23.            100           100                                              33.            100           100                                              36.            100           100                                              44.            100           95                                               49.            100           100                                              55.            100           95                                               57.            95            90                                               64.            100           100                                              71             100           95                                               73.            100           100                                              75.            100           100 - 78.                                                                             100  100 - 85. 100  90                   91.            100           90                                               97.            100           95                                               100.           100           95                                               106.           100           100                                              113.           100           85                                               115.           95            80                                               119.           95            85                                               126.           90            80                                               134.           95            85                                               136.           100           95                                               137.           100           95                                               143.           95            85                                               147.           90            85                                               ______________________________________                                    

TEST EXAMPLE 7

Each powder containing (3), (6), (11). (13), (16), (18), (23), (24),(25), (26), (32), (37), (42), (47), (54), (60), (63), (68), (71), (74),(79), (84), (89), (96), (102), (105), (110), (116), (120), (127) and(131) which is prepared by the Reference Example 7 is uniformlysprinkled at the ratio of 2 g/m² on the bottom of a tall glass vesselhaving a diameter of 14 cm and then butter is coated on the wall of thevessel leaving the portion of 1 cm height from the bottom. A groupconsisting of 10 imagines of Blattella germanicas are placed on thebottom of the vessel. After the group is put into contact with thepowder for 30 minutes, it is transferred into a clean vessel. Afterthree days, more than 80% of germanicas are killed with any of powders.

What is claimed is:
 1. Cyclopropane carboxylic acid ester derivativesand optical and geometrical isomers thereof expressed by the generalformula: ##STR226## wherein R₁ represents hydrogen atom or methyl group,R₂ represents alkyl group, alkenyl group, haloalkyl group, haloalkenylgroup having 1-6 carbon atoms and a group selected from groups of thegeneral formulae (II), (III) and (IV): ##STR227## in which n is aninteger of 2-5, R₄ represents methyl group, chlorine atom or methoxygroup, and R₃ represents a group selected from the groups of the generalformulae (V), (VI), (VII), (VIII), (IX) and (X): ##STR228## in which Xrepresents oxygen atom or vinylene group, R₅ represents allyl group,propargyl group, benzyl group, phenoxy group or 2,2-dichlorovinyloxygroup, R₆ represents hydrogen atom, methyl group or haloen atom, R₇represents hydrogen atom, cyano group, ethynyl group or trifluoromethylgroup and m is an integer of 1-2, R₈ represents allyl group orpentadienyl group, Y represents oxygen atom or methylene group, R₉represents hydrogen atom, methyl group, allyl group or halogen atom andR₁₀ represents methyl group or halogen atom.
 2. Cyclopropane carboxylicacid ester derivatives and optical and geometrical isomers thereofexpressed by the general formula: ##STR229## wherein R₁ representshydrogen atom or methyl group, R₂ represents alkyl group, alkenyl group,haloalkyl group, haloalkenyl group having 1-6 carbon atoms and a groupselected from the groups of the general formulae (II), (III) and (IV):##STR230## in which n is an integer of 2-5, R₄ represents methyl group,chlorine atom or methoxy group, and R₃ represents the general formula:##STR231## wherein R₇ represents hydrogen atom, cyano group, ethynylgroup or trifluoromethyl group.
 3. The cyclopropane carboxylic acidester derivatives and steric isomers thereof set forth in claim 1wherein R₁ is a hydrogen atom.
 4. The cyclopropane carboxylic acid esterderivatives and the steric isomers thereof claimed in claim 1 wherein R₁is a methyl group.
 5. Compound claimed in claim 2 expressed by theformula: ##STR232##
 6. Compound claimed in claim 2 expressed by theformula: ##STR233##
 7. Compound claimed in claim 2 expressed by theformula: ##STR234##
 8. Compound claimed in claim 2 expressed by theformula: ##STR235##
 9. Compound claimed in claim 2 expressed by theformula: ##STR236##
 10. Compound claimed in claim 2 expressed by theformula: ##STR237##
 11. Compound claimed in claim 2 expressed by theformula: ##STR238##
 12. Compound claimed in claim 2 expressed by theformula: ##STR239##
 13. Compound claimed in claim 2 expressed by theformula: ##STR240##
 14. Compound claimed in claim 3 expressed by theformula: ##STR241##
 15. Compound claimed in claim 3 expressed by theformula: ##STR242##
 16. An insecticidal composition comprising an inertcarrier and an insecticidally effective amount of a compound as setforth in claim
 1. 17. An insecticidal composition according to claim 16which includes as an auxiliary agent a syngergistically effective amountof a compound selected from the group consisting of piperonyl butoxide,octachlorodipropyl ether, N-octylbicycloheptene dicarboxyimide andN-octyl-1-isopropyl-4-methylbicyclo-[2,2,2]-oct-5-en-2,3-dicarboxyimide.18. A compound of the formula ##STR243## wherein, R¹ is hydrogen orcyano; andR² is lower alkyl of 1 to 6 carbon atoms, lower haloalkyl of 1to 6 carbon atomes, lower alkenyl of 2 to 6 carbon atoms, lowerhaloalkenyl of 2 to 6 carbon atoms and a group selected from the groupsof the general formulae (II), (III), and (IV): ##STR244## in which n isan integer of 2-5, R₄ is a methyl group, chlorine atom or methoxy group.19. A method for combatting pests which comprises treating said pestwith a pesticidally effective amount of a compound of the formula amountof a ##STR245## wherein, R¹ is a hydrogen or cyano; andR² is a loweralkyl of 1 to 6 carbon atoms, lower haloalkyl of 1 to 6 carbon atoms,lower alkenyl of 2 to 6 carbon atoms, lower haloalkenyl of 2 to 6 carbonatoms and a group selected from the groups of the general formulae (II),(III), and (IV): ##STR246## in which n is an integer of 2-5, R₄ is amethyl group, chlorine atom or methoxy group.